CN101654495A - Preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel - Google Patents
Preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel Download PDFInfo
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- CN101654495A CN101654495A CN200910023122A CN200910023122A CN101654495A CN 101654495 A CN101654495 A CN 101654495A CN 200910023122 A CN200910023122 A CN 200910023122A CN 200910023122 A CN200910023122 A CN 200910023122A CN 101654495 A CN101654495 A CN 101654495A
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Abstract
The invention discloses a preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel; diene propyl methyl dodecyl, tetradecyl, hexadecyl and stearyl ammonium bromide are taken as a hydrophobic segmer monomer to be copolymerized with methacrylic acid, N, N-methylene bisacrylamide is taken as a cross-linker, azo-bis-iso-butyl amidine hydrochloride is taken as an initiator, a vacuum line is used for carrying out desaeration to prepare the hydrophobic segmer modified polymethyl acrylic acid pH responsive gel; the invention prepare the hydrophobic segmer modified polymethyl acrylic acid pH responsive gel by adopting water soluble quaternary ammonium salt containing diene propyl alkyl and taking water as the medium, and has the advantage of good environment protection property.
Description
Technical field
The present invention relates to polyelectrolyte responsiveness high-molecular gel preparing technical field, particularly the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel.
Background technology
Polyelectrolyte responsiveness high-molecular gel has some particular performances, therefore is widely used in the technology such as electrical signal field, bioseparation, medicament slow release.This gellike can be under the change of external environment such as temperature, pH, electrolyte environment etc. reversible generation volume change.The research of pH responsiveness high-molecular gel at present receives much concern, especially as medicinal slow release agent.
The pH responsive gel is divided into weak base type polymeric matrix or weak-type polymeric matrix mostly.When gel was soaked in the polar system, gel was subjected to the osmotic pressure influence that gegenion produces in the system along with the variation of degree of ionization, can take place from tightening state to the swollen phase transition behavior.
By in weak acid or weakly alkaline gel backbone, introducing a kind of good method that hydrophobic segment is the control gel swelling.When not having electric charge in the gel, the hydrophobic segment in the side chain can flock together.After gel ionization swelling, crosslinked action can take place in the hydrophobic group on the gel side chain.
Philips seminar has done number of research projects in this regard.They adopt vinylformic acid and n-alkyl acrylate (n=8,12,18) monomer to prepare serial weak-type hydrophobic segment modified gel; Studies show that when the molar fraction of n-alkyl acrylate less than 20% the time, during the complete ionization of hydrophobic segment, the same swollen state that shows with unmodified gel polyacrylic acid.Subsequently, they adopt above-mentioned system, have prepared the weak-type hydrophobic segment modified gel of serial different dissociation degree, have studied opposition effect between hydrophobic segment and electrostatic interaction by the change of ionic strength and hydrophobic segment; Play an important role in the swelling that accumulates in gel of hydrophobic segment, the length that increases hydrophobic segment makes that the reactive force of hydrophobic segment increases in the gel, has caused the swelling of gel and has carried out to alkali systems.They adopt vinylformic acid, n-alkyl acrylate (n=8,12,18) is monomer, and N,N methylene bis acrylamide is a linking agent, has prepared serial gel copolymer, and adopts small-angle neutron scattering (SANS) in D20 its swelling property to be studied.
Han Siyou and people such as Ritchie mention in patent and adopt massfraction is that the polymethyl acid unit of 20%-65% and C1-C18 alkyl acrylic ester units that massfraction is 80%-35% prepare pH responsiveness polymer.People such as Liu Yuyang adopt hydrophobic monomer ethyl acrylate (AAEHE) and methacrylic acid by the UV-irradiation solution polymerization serial hydrophobic chain modified polymethyl sour water gel (HMPMAA), and it is studied as the controllable release matrix.At present, be used to produce the crosslinked compound of reversible hydrophobicity and mostly be oil-soluble monomers such as esters of acrylic acid, so system need adopt organic solvent.All there is poorly water-soluble in these class methods, the shortcoming of environmental-protecting performance difference.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel is provided, this method is medium with water, has the advantage of good environmental protection.
For achieving the above object, the technical solution used in the present invention is:
The present invention is the hydrophobic segment monomer with diallyl methyl 12,14,16, octadecyl bromination ammonium, with the methacrylic acid copolymerization, adopt N, the N-methylene-bisacrylamide is as linking agent, azo-bis-isobutyrate hydrochloride is as initiator, by the vacuum line processing that outgases, the preparation hydrophobic segmer modified polymethyl acrylic acid pH responsive gel.
The preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel may further comprise the steps:
The first step, diallyl methyl alkyl brometo de amonio (CCx) and methacrylic acid (MAA) were made monomer in 5: 95 in molar ratio～20: 80, linking agent N, the N-methylene-bisacrylamide accounts for 1.0%～2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.0%～2.5% of monomer molar total amount, and whole system concentration is 1.0mol/L～3.0mol/L, all is dissolved in the water, system is even behind the 2-5min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 70-75 ℃ of reaction, behind the question response 3-6h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCCx-MAA).
Since the present invention adopts be have necessarily water-soluble, contain the diallyl alkyl quaternary ammonium salts and prepare hydrophobic segmer modified polymethyl acrylic acid pH responsive gel, so present method is a medium with water, have the advantage of good environmental protection.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment one
The first step, diallyl methyl dodecyl bromination ammonium (CC12) and methacrylic acid (MAA) were made monomer in 15: 85 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.0% of monomer molar total amount, and whole system concentration is 1.0mol/L, all is dissolved in the water, system is even behind the 2min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 70 ℃ of reactions, behind the question response 6h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC12-MAA).
Embodiment two
The first step, diallyl methyl Tetradecylammonium bromide (CC14) and methacrylic acid (MAA) were made monomer in 20: 80 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 1.5% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.7% of monomer molar total amount, and whole system concentration is 2.0mol/L, all is dissolved in the water, system is even behind the 3min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 75 ℃ of reactions, behind the question response 5h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC14-MAA).
Embodiment three
The first step, diallyl methyl hexadecyl brometo de amonio (CC16) and methacrylic acid (MAA) were made monomer in 10: 90 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.0% of monomer molar total amount, and whole system concentration is 2.0mol/L, all is dissolved in the water, system is even behind the 4min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 74 ℃ of reactions, behind the question response 3h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC16-MAA).
Embodiment four
The first step, diallyl methyl hexadecyl brometo de amonio (CC16) and methacrylic acid (MAA) were made monomer in 15: 85 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 1.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 2.5% of monomer molar total amount, and whole system concentration is 3.0mol/L, all is dissolved in the water, system is even behind the 5min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 72 ℃ of reactions, behind the question response 4h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC16-MAA).
Embodiment five
The first step, diallyl methyl octadecyl bromination ammonium (CC18) and methacrylic acid (MAA) were made monomer in 5: 95 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 2.5% of monomer molar total amount, and whole system concentration is 3.0mol/L, all is dissolved in the water, system is even behind the 5min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 73 ℃ of reactions, behind the question response 5h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC18-MAA).
Through evidence, present method is medium with water, has the advantage of good environmental protection, is a kind of preparation method of novel hydrophobic segmer modified polymethyl acrylic acid pH responsive gel.
Claims (6)
1, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel is characterized in that: may further comprise the steps:
The first step, diallyl methyl alkyl brometo de amonio (CCx) and methacrylic acid (MAA) were made monomer in 5: 95 in molar ratio～20: 80, linking agent N, the N-methylene-bisacrylamide accounts for 1.0%～2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.0%～2.5% of monomer molar total amount, and whole system concentration is 1.0mol/L～3.0mol/L, all is dissolved in the water, system is even behind the 2-5min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 70-75 ℃ of reaction, behind the question response 3-6h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCCx-MAA).
2, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel according to claim 1 is characterized in that: may further comprise the steps:
The first step, diallyl methyl dodecyl bromination ammonium (CC12) and methacrylic acid (MAA) were made monomer in 15: 85 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.0% of monomer molar total amount, and whole system concentration is 1.0mol/L, all is dissolved in the water, system is even behind the 2min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 70 ℃ of reactions, behind the question response 6h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC12-MAA).
3, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel according to claim 1 is characterized in that: may further comprise the steps:
The first step, diallyl methyl Tetradecylammonium bromide (CC14) and methacrylic acid (MAA) were made monomer in 20: 80 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 1.5% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.7% of monomer molar total amount, and whole system concentration is 2.0mol/L, all is dissolved in the water, system is even behind the 3min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 75 ℃ of reactions, behind the question response 5h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC14-MAA).
4, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel according to claim 1 is characterized in that: may further comprise the steps:
The first step, diallyl methyl hexadecyl brometo de amonio (CC16) and methacrylic acid (MAA) were made monomer in 10: 90 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 1.0% of monomer molar total amount, and whole system concentration is 2.0mol/L, all is dissolved in the water, system is even behind the 4min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 74 ℃ of reactions, behind the question response 3h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC16-MAA).
5, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel according to claim 1 is characterized in that: may further comprise the steps:
The first step, diallyl methyl hexadecyl brometo de amonio (CC16) and methacrylic acid (MAA) were made monomer in 15: 85 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 1.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 2.5% of monomer molar total amount, and whole system concentration is 3.0mol/L, all is dissolved in the water, system is even behind the 5min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 72 ℃ of reactions, behind the question response 4h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC16-MAA).
6, the preparation method of hydrophobic segmer modified polymethyl acrylic acid pH responsive gel according to claim 1 is characterized in that: may further comprise the steps:
The first step, diallyl methyl octadecyl bromination ammonium (CC18) and methacrylic acid (MAA) were made monomer in 5: 95 in molar ratio, linking agent N, the N-methylene-bisacrylamide accounts for 2.0% of monomer molar total amount, the initiator azo-bis-isobutyrate hydrochloride accounts for 2.5% of monomer molar total amount, and whole system concentration is 3.0mol/L, all is dissolved in the water, system is even behind the 5min
In second step, the needle tubing of employing 2mL adds the above-mentioned solution of 2mL volume in Glass tubing, adopt the vacuum line degassing 3 times, tube sealing, and in 73 ℃ of reactions, behind the question response 5h, open pipe takes out solid, and cuts into slices immediately,
The 3rd step placed ethanol/water (1: 1) mixed solvent with solid slice, removed unreacted monomer and no cross-linked polymer, placed 30 ℃ of vacuum drying ovens dry, obtained hydrophobic segmer modified polymethyl acrylic acid pH responsive gel (PCC18-MAA).
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| CN113583653A (en) * | 2020-04-30 | 2021-11-02 | 爱森（中国）絮凝剂有限公司 | Novel aqueous fracturing fluid composition and fracturing method using the same |
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| CN1318463C (en) * | 2003-09-24 | 2007-05-30 | 天津工业大学 | Environment responding aquogel copolymer and its prepn |
| CN100341908C (en) * | 2005-03-18 | 2007-10-10 | 中国科学院理化技术研究所 | Template copolymerizing synthetic process of semi-intercrossing network reversible pH sensitive aquagel |
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| CN113583653A (en) * | 2020-04-30 | 2021-11-02 | 爱森（中国）絮凝剂有限公司 | Novel aqueous fracturing fluid composition and fracturing method using the same |
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